Condensation products and process of making same



Patented Apr. 7, 1936 UNITED STATES PATENT OFFICE CONDENSATION PRODUCTS AND PROCESS OF MAKING SAME land No Drawing. Application February 9, 1935, Serial 8 Claims.

This invention relates to the manufacture of condensation products having capillary activity wherein an aromatic amine, which contains at least one sulfonic acid-hydroxyalkyl-amide group or sulfonic acid-hydroxyalkylaryl-amide group, if desired e'sterified with sulfuric acid, is acylated with an aliphatic carboxylic acid containing more than 3 carbon atoms and, if desired, is esterified at the free hydroxyl group with sulfuric acid.

The aromatic amines containing at least one sulfonic acid-hydroxyalkylor sulfonic acid-hydroxyalkyl-aryl-amide group may be made by known methods, for example by causing a nitro compound of the benzene series which is substituted in, another position than in ortho-position to the nitro-group by a radical of the general formula BOiN in which R stands for hydrogen, alkyl, aralkyl or aryl radicals, to react with an alkylene halogenhydrin, or by causing a nitrated aryl-sulfonic acid chloride of the benzene series to react with an hydroxyalkylamine or an arylhydroxyalkylamine and subsequent reduction of the nitro-group to the amino-group.

As nitro-compounds of the benzene series which are substituted in another position than in orthoposition to the nitro-group by a radical of the general formula In Switzerland February 13, 193% rohydrins, the trimethylene chlorohydrin, amonochlorohydrin, a-monobromohydrin, p-monochlorohydrin, dichlorohydrin and the like.

As nitrated arylsulfonic acid chlorides of the benzene series there come into consideration those products which correspond to the just cited nitrated arylsuliamides and the equivalents thereof.

Among the hydroxyalkylamines there may be named ethanolamine and diethanolamine, and among the arylhydroxyalkyl-amines N-mono-hydroxyethyl-aniline, N-monohydroxy-ethyl-metaor N-monohydroxy-ethyl-para-toluidine and the like.

Esterification of the free hydroxyl-group may be carried out by means of sulfuric acid, chlorosulfonic acid or agents containing one or other of these acids. The esterification may precede or follow the conversion of the nitro-compounds into the amino-compounds or acylamino-compounds. For the acylation are suitable aliphatic saturated or unsaturated carboxylic acids containing more than 3 carbon atoms, which acids may he unsubstituted or may contain hydroxyl-groups or halogen atoms. Among others, the following come into question: butyricacids, such as n-but'yric acid and isobutyric acid, crotonic acids and chlorocrotonic acids, valerianic acids, such as n-valerianic acid and isopropyl acetic acid, caproic acid, caprylic acid, capric acid, lauric acid, palmitic acid, stearic acid, hivdroxy-stearic acids, chlorostearic acids and bromo-stearic acids, oleic acid, ricinoleic acid and the like, further their natural or artificial mixtures. There come also into question such acids whose chain is interrupted by an organogenic element (cf. Lehrbuch der organischen Chemie by Paul Karrer, Leipzig, 1928, page 4: Zusammensetzung und analyse organischer verbindungen line 4i) which in respect to hydrogen'is not higher than trivalent. These elements are oxygen,- sulfur and nitrogen. Acids whose chain is interrupted by an organogenic element are, for example, stearoyl-glyc ine (cf. Birchemische Zeitschriit, vol. 40,1912, page 4H3; further ethers from higher alcohols and halogen acetic acids, such as the ether from cetyl alcohol and mono-chloroacetic acid, the thio-ether from cetyl mercaptan and mono-chloroacetid acid, or the ester from stearic acid and glycolic acid. The same products are obtained, whether one uses the free acid, its esters, such as its glyceride which is found, for instance in nature as beef tallow, coconut oil, olive oil, fish oil and hardened fish oil, or its halides, or its anhydride. The acylation may follow the esterification of the hydroxyl group, preferably in aqueous solution by means of a halide of the acid in presence of an alkali or another agent that binds acid. However, it is also possible to acylate before esterifying and in this case the procedure may be by way of fusing the amino-compound with the free acid or an ester thereof, for example a glyceride.

The condensation products obtainable by this invention are bright powders, easily soluble in water. They correspond to the general formula in which R1 represents an aliphatic radical containing at least 3' carbon atoms, R: an alkylene radical containing not more than 3 carbon atoms, and Rs hydrogen, alkyl, aralkyl or aryl, and in which the group R:O-SO:H

SOIN

does not stand in ortho-position to the group. The solutions are suitable, according to the aliphatic acid used, for use as wetting agents, penetrating agents, washing agents and emulsifiers. Among these products those claim quite generally the greater interest which derive from acids with straight chains consisting of at least 10 carbon atoms. Those products which are obtained, for example by use of lauric acid or oleic acid are characterized by a good washing action, as well as a good wetting action. Moreover, they lend to the treated textiles, for example to artificial silk, a soft, fleecy grip. This is for example the case with products derived from stearic acid. The products are generally fully stable towards the constituents imparting hardness to water, to acids and alkalies. They .may be used in neutral, acid or alkaline baths, as well as in baths containing much salt. They are suitable not only as washing and wetting agents but also as paste-forming agents .for dyestuffs insoluble in water and, therefore, find use in dyeing with vat-dyestuffs, or in dyeing cellulose acetate silk. Furthermore, they are suitable for use in acid baths for dyeing wool, since they promote uniform exhaustion and a levelling effect.

The following examples illustrate the invention, the parts being by weight:-

Example 1 neutralized. By reduction with iron in an aqueous solution by usual methods; thereis obtained the amino-compound of the probable formula The 1-nitro-3-benzenesulfonic acid-N-hydroxyethylanilide used in this example can be made as follows:

278 parts of 1-nitrobenzene-3-sulfonic acidanilide, 267 parts of a sodium hydroxide solution of 30 per cent. strength, 1'76 parts of ethylenechloro-hydrin and 1000 parts of water are heated together in an autoclave at 120-130 C. After cooling, the solid matter is washed with water. The 1-nitro-3-benzenesulfonic acid-N-hydroxyethylanilide is thus obtained in good yield.

(a) 440 parts of the amino-compound obtained as described above are dissolved in 1000 parts of water, 82 parts of anhydrous sodium acetate are added and then, at 5-15 C., while stirring well, 300 parts of oleic acid chloride are gradually dropped in. The whole is then neutralized and stirred at about C. for 2-3 hours. The pasty product thus formed may, if desired, be used directly in this form. It dissolves clearly in water and the solution has good wetting and washing properties. The new product corresponds very probably to the formula The isomeric product deriving from the l-aminobenzenei-sulfonic acid possesses similar properties.

(b) 440 parts of the amino-compound described above are dissolved in 1000 parts of water and 82 parts of anhydrous sodium acetate are added. The mixture is stirred at 5-l0 C. with 218 parts of lauric acid chloride and then further treated. as described under a. The product shows properties similar to those of the product made from oleic acid chloride.

(0) By substituting for the oleic acid chloride 302 parts 01' stearic acid chloride and operating as described under a, there is obtained a similar product which is particularly suitable as a softening agent.

Example 2 parts of concentrated .solution of sodiumchloride, whereby, after some stirring in the cold, the sodium salt of the sulfuric acid ester of l-nitrod-benzene-sulfonic' acid-hydroxyethylamide is obtained. This is reduced, as described in Example 1, to the amino-derivative of the probable formula Into a solution of 380 parts of this amino-body and 82 parts of anhydrous sodium acetate in 800 parts of water there are dropped, at -15 C., 300 parts of oleic acid chloride. The whole is then neutralized with sodiumhydroxide and stirred for 2-3 hours at room temperature. The product, which may be used in the form of a paste or of a dry powder, has good wetting, washing and levelling properties. It corresponds very probably to the formula If, instead of the .oleic acid chloride 218 parts of lauric acid chloride are used, without otherwise altering the operation there is obtained a product in the form of a paste which is very effective as a, washing and wetting agent. This product can also be used as an addition to dyebaths. It corresponds very probably to the formula The corresponding product from the stearic acid corresponds very probably to the formula The products from lower acids such as, for example,

are intended to be used as wetting and dispersing agents. 4

Products having a similar effect are also obtained when treating the 1-nitro-3-benzenesulfonic acid-hydroxyethylamigia, "prior to the reduction and acylation with the aliphatic acid, with an aralkylating agent, such as benzyl chloride, ortho-or pana-chlorobenzyl chloride, or wchloro-I-methylnaphthalene and the like. same products are also obtained when treating of oleic acid chloride.

The.

the reduced and acylated products with the aralkylating agents.

Example 3 If, instead of the hydroxyethylamide used in Example 2 that of 1-chloro-4-nitro-2-benzenesulfonic acid is used, there is obtained, by treatment with sulfuric acid and subsequent reduction, an amino-body which probably has the following formula SOzNHCHaCHaOSOaH -SO:|-N

in which R1 represents an aliphatic radical having at least carbon atoms in a straight chain, R2 an alkylene radical having not more than 3 carbon atoms, and R3 is a member of the group consisting of hydrogen, alkyl, aralkyl and aryl, and in which the group m-o-som SOzN does not stand in ortho-position to the i H-N--R; group, which products are light colored powders, easily soluble in water and suitable as wetting agents, penetrating agents, washing agents and emulsifiers in the textile industry.

2. As textile assistants, the-condensation products ofthe general formula 0 H--N -R| m-o-som in which R1 represents an aliphatic radical having at least 10 carbon atoms in a. straight chain, and R2 an alkylene radical having not more than 3 carbon atoms, and in which the group R:0-S0|H" does not stand in ortho-position to the group, which products are light colored powders, easily soluble in water and suitable as wetting agents, penetrating agents, washing agents and emulsifiers in the textile industry.

3. As textile assistants, the condensation products of the general formula atyl does not stand in ortho positlon to the group, which products are light colored powders,

easily soluble in water ,and suitable as wetting agents, penetrating agents, washing agents and emulsifiers in the textile industry.

4. As textile assistants, the condensation products of the general formula CHg-CHz-O-S OaH in which R represents an aliphatic radical having at least 10 carbon atoms in a straight chain, which products are light colored powders, easily soluble inwater and suitable as wetting agents, penetrating agents, washing agents and emulsifiers in the textile industry.

5,. As textile assistants, the condensation prod-' nets of the general formula f rr-N-o-R in which R represents an aliphatic radical having at least ll carbon atoms in a straight chain, which products are light colored powders, easily soluble in water and suitable as wetting agents, penetrating agents, washing agents and emulsifiers in the textile industry.

6. As a textile assistant, the condensation product of the formula CHz-CHr-O-S 01H which product is a light colored powder, easily soluble in water and suitable as wetting agent, penetrating agent, washing agent and emulsifier in the textile industry.

7. As a textile assistant, the condensation product of the formula which product is a-light colored powder, easily soluble in water and suitable as wetting agent, penetrating agent, washing agent and emulsifier in the textile industry.

8. As a textile assistant, the condensation product of the formula which product is a light colored powder, easily soluble in water and suitable as wetting agent, penetrating agent, washing agent and emulsifier in the textile industry.

FRIEDRICH FELIX. J AKOB SCHEDDEGGER. 

